Pi-allyl transition metal adducts with lewis acids and/or lewis bases



U.S. Cl. 260-429 29 Claims ABSTRACT OF THE DISCLOSURE Adducts ofvr-allyl transition metal compounds and Lewis acids and/ or Lewis bases.Particularly claimed are 1:1:1 adducts of a Lewis base, a Lewis acid anda ar-allyl transition metal compound. These products are suitable foruse to catalyze the cyclo-oligomerization of mono and diolefins.

This invention relates to the production of vr-allyl transition metalcompounds. It more particularly refers to a novel method of producingsuch compounds as well as to the compounds so produced and derivativesthereof.

This specification discloses a novel group of 1r-allyl compounds whichare free of other ligands and have a metal constituent of Groups IVb,Vb, VIb and VIII of the Periodic Table. It is further disclosed in thisspecification a process for producing these novel compounds by reactinga water-free transition metal compound with an allyl compound of a metalof Groups Ia, Ila, IIb and IIIa at a temperature of about lO C. to 100C. under an inert gas. The allyl group may suitably be a straight chainof a cyclic compound having 3 carbon atoms in a plane containing allylicunsaturation distributed amongst these 3 carbon atoms. The compounds ofthis invention may also exist in the form of a salt with substantiallyany appropriate anion. The compounds and salts of this invention haveutility as catalysts for the cyclooligomerization of monoand diolefins.Specifically, exemplary compounds produced by the practice of thisinvention include tris-(wr-allyl)-chromium, 1r-a1lyl palladium chloride,1r-cyclooctatrienyl-nickel-acetate and adduct of vr-allyl-nickel-iodideand triphenylphosphine.

The compounds of this invention are 1r-allyl or substituted allyltransition metal compounds, their salts and their adducts with variousLewis acids or bases. These compounds, salts and/or complexes are freefrom other ligands than these specified.

This application is a continuation-in-part application of applicationSerial No. 272,881, filed April 15, 1963, now abandoned; applicationSerial No. 387,990, filed August 6, 1964, and application Serial No.387,826, filed August 6, 1964, now Patent Number 3,379,706, issued April23, 1968.

1r-Allyl transition metal compounds were first made in 1959 by Smidt andHefner, see Angewandte Chemie 71,284 (1959). Further allyl metalcompounds have been made by H. B. Joanssen, J. Amer. Chem. Soc. 80, 2586(1958); R. Huttel u. I. Kratzer, Angew, Chem. 71,456 (1959); I. I.Moiseev, E. A. Fedorowskaya u.Y.K. Syrkin, I. Anorg. Chem. (Russ) 4,2641 (1959). These products generally contained additional ligandsbesides the 1r-allyl group therein.

Wilke and Bogdanovic showed, in Angewandte Chemie, vol. 73 (1961), p.756, that it is possible to produce carbonyl-free bis-ar-allyl nickel bythe reaction of anhydrous nickel bromide and allyl magnesium chloride.Thus, for

3,468,921 Patented Sept. 23, 1969 the first time there was prepared a1r-allyl transition metal compound containing no other ligands than1r-allyl groups.

It is an object of this invention to provide an improved process forpreparing 1r-allyl transition metal compounds.

It is another object of this invention to provide improved processes forpreparing novel derivatives of 1r-ally1 transition metal compounds.

It is a further object of this invention to provide a novel series ofcarbonyl-free 1r-allyl transition metal compounds.

It is a still further object of this invention to provide novelderivatives of 1r-allyl transition metal compounds.

Other and additional objects of this invention will become apparent froma consideration of this entire specification, including the claimsappended hereto.

In accord with and fulfilling these objects, one aspect of thisinvention resides in the dicovery that 1r-allyl transition metalcompounds containing no other ligands than 1r-allyl groups can bemanufactured in commercial quantities and of a purity sufficient for theintended use, described below, by the reaction of a water-free compoundof a transition metal of Groups IVb, Vb, VIb or VIII of the PeriodicTable with an allyl compound of a second, non-transition metal of GroupsIa, Ila, IIb, or IIIa, provided that the reaction is carried out in thesubstantial absence of water and under a substantially inert gasblanket.

As used herein, the Periodic Table referred to is that which is used bythe International Union of Pure and Applied Chemistry.

The 1r-3llyl transition metal compounds produced by the process of thisinvention show utility as catalysts for the cyclooligomerization of1,3-diolefins, particularly butadiene, to produce cyclododecatri'ene.

w-Allyl transition metal compounds produced according to the practice ofthis invention correspond to the general formula:

l a lita 1?; QIQIQf Me wherein R to R may in general be any organicradical or hydrogen. It may also be that the allyl group may be part ofa closed ring system, in which case R and R, will together form adivalent organic bridging radical such as, for example, an alkylenegroup. Me is any of the transition metals generally described above andn is an integer of 1 to 4.

In particular, the R to R groups are suitably hydrogen, alkyl,cycloalkyl, aralkyl, aryl, alkylene (in the case of the allyl groupbeing part of a closed ring system) or cycoalkylene (in the case of theallyl group being part of a closed bicyclo ring system). Exemplary ofthe substituent groups R through R set forth above, there are methyl,ethyl, propyl, butyl, 2-ethylhexyl, nonyl, dodecyl, octadecyl,cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, phenyl, tolyl,naphtyl, and t-butyl phenyl. It is within the scope of this inventionthat the terminal carbon atoms of the allyl group may be joined by abridging divalent aliphatic hydrocarbon such as, for example, analkylene or alkenylene group to form a saturated or unsaturated ringcompound containing at least one planar allyl grouping therein. Thisring compound may itself be substituted as, for example, by one or morelower alkyl groups having up to about 6 carbon atoms in normal orisomeric configuration. Where a ring containing allyl moiety is utilizedin the pratice of this invention, such ring may contain between about 3to 12 carbon atoms therein and may, in addition, as set forth above,have one or more alkyl substituents thereon.

The transition metals generally described above are exemplified bytitanium, vanadium, chromium, iron, cobalt, zirconium, niobium,molybdenum, palladium, tantalum, platinum, tungsten, thorium and nickel.

It has been discovered that the substituted allyl radicals, e.g. crotyl,methallyl, cyclooctenyl, etc. form much more stable ar-allyl transitionmetal compounds than unsubstituted allyl, i.e., where R to R are allhydrogen. It is therefore preferred, particularly in the case of nickelcompounds, to provide at least one of the R to R substituents as ahydrocarbon.

As noted above, one of the reactants used to produce 1r-allyl transitionmetal compounds according to this invention is an organometallic moiety.It is particularly preferred in the practice of this invention that themetal moiety of this organometallic compound be chosen from Groups Ia,11a, 11b and IIIa metals. Of particular interest are the alkali metals,alkaline earth metals, boron, aluminum, mercury and zinc. The alkalimetals are exemplified by sodium, potassium and lithium. The alkalineearth metals are exemplified by magnesium, calcium, beryllium,strontium, and barium.

The reaction according to the present invention is preferably carriedout in a liquid reaction medium which is inert towards both the startingmaterials and the reaction products. Solvents which show some solventpower for the reaction components may be used to advantage, aliphatic,cyclic or aromatic ethers being especially preferred.

Likewise, there may be used to advantage transition metal compoundswhich are at least slightly soluble in the reaction medium, even thoughsolubility may be quite low. The halides or acetylacetonates oftransition metals have, for example, proved particularly successful, butother compounds can also be employed. Particularly suitable asorgano-metallic components for introducing the aforesaid allyl-radicalare compounds of alkali and alkaline earth metals, but the correspondingcompounds of Zinc or mercury or boron or aluminum can also be employed.

The organo-conrpounds of the above elements are obtained by knownmethods; in the simplest case, for example, allyl magnesium chloride isobtained by allyl chloride and magnesium. It has, however, been foundthat in many cases it is unnnecessary to produce the organometalcompounds separately before the reaction with the transition metalcompounds; thus, the desired reaction also succeeds if, for example,crotyl chloride is reacted in the presence of the transition metalcompounds with,

for example, magnesium. The necessary magnesium compound is formed as anintermediate, but this immediately reacts with the transition metalcompound to give the desired 1r-allyl compound of the transition metal.

Reaction is effected at temperatures between-400 and 100 C., dependingupon the stability of the compounds produced in accordance with theinvention, but temperatures below 0 C. are usually employed.

Another aspect of this invention resides in the 1r-ally1 transitionmetal compounds produced by the above-described process.

The majority of the novel compounds are readily volatile and this isparticularly true of compounds with low hydrocarbon radicals. Isolationcan thus be effected by distillation or sublimation. In other cases itis recommended to distill off the solvents employed for the reaction andto extract the desired products from the residue with, for example,hydrocarbons. Any salts formed as by-products remain behind undissolved.In the majority of cases, the novel compounds crystallise outsatisfactorily.

The transition metal compounds of the present invention are highlyefficient catalysts for reactions of unsaturated hydrocarbons, inparticular 1,3-diolefins and acetylenes. Bisw-methallyl nickel producedin accordance with the invention, for example, readily reacts withbutadine to form cyclododecatriene-( 1,5,9)

The invention can be illustrated by the following examples which are inno way limitative:

Example 1 20 g.=0.09 mol anhydrous nickel bromide are suspended in 150cc. absolute ether and reacted at 20 C. with 700 cc. of a solution (0.5standard) of crotyl magnesium chloride (0.35 mol) in ether. The ethersolution turns deep yellow. After four hours the ether is distilled offat 200 mm. Hg via a low-temperature column. 10.7 g. of a nickel compoundin the form of yellow crystals, corresponding to the composition NiC Hand representing the previously unknown biS-vr-CrOtYl nickel, can besublimated off from the residue in high vacuum. Yield 70% of theory.This compound, too, is extremely sensitive to air and must be kept incold storage.

Example 2 Reaction is carried out as in Example 1, but the aforesaidnickel compound is reacted with a solution of methallyl magnesiumchloride. The previously unknown bismethallyl nickel of the compositionNiC H is obtained in yields of 50 to 60% of theory in the form of yellowcrystals. The compound is sensitive to air and must be kept in coldstorage.

Example 3 l2 g.=0-.09 mol anhydrous nickel bromide and 24 g.=l g. atommagnesium chips are introduced into 300 cc. absolute ether. Over aperiod of 6 hours, 30 g.=0.33 mol methallyl chloride in 200 cc. absoluteether are added dropwise to this mixture. A yellow-coloured ethersolution, from which the bis-vr-methallyl nickel is isolated inaccordance with Example 1 or 2, is obtained. Yield 50-60% of theory.

Example 4 575 cc. of an 0.46 molar solution of allyl magnesium chloride(0.264 mole) in ether are cooled to C. and in the course of 2 hoursmixed with a solution of 14 g.=0.087 mol iron (III) chloride in cc.ether. The ether solution turns deep yellowish-brown. When the reactionhas finished, the ether is drawn off in vacuo at 30 to 50 C. The residueis extracted at -30 C. with pentane. The deep brown pentane extract iscooled to 80 C., whereby gold crystals separate out. These are freedfrom the last traces of solvent in high vacuum at 80 C. The crystals arevolatile in high vacuum at 0 C. The previously unknown tris-w-allyl ironof the composition FeC H is found. Yield 10 to 20% of theory.

The compound can only be stored at low temperatures. At room temperaturethe crystals decompose explosively. The compound is sensitive to air.

Example 5 Reaction is carried out in accordance with Example 3 but iron(III) acetylacetonate is employed. Yield 20% of theory.

Example 6 7.12 g.=0.02 mol cobalt (III) acetylacetonate are suspended in100 cc. absolute ether. The suspension is cooled to 80 C. and cc. of asolution (0.5 molar) of allyl magnesium chloride (0.09 mol) are added. Adeep orange solution is obtained. The green acetylacetonate slowlydisappears. When the reaction has finished, the ether is drawn off at0.1 to 1 mm. Hg and 60 C. The residue is extracted at 60 C. with pentaneand the extract is cooled to 80 C. Reddish-gold crystals, which whenfreed in high vacuum from the last traces of pentane, correspond to thecomposition CoC I-L and represent the hitherto unknown tris-1r-allylcobalt, separate out. Yield 45 to 50% of theory.

The compound must be stored at low temperatures as it begins todecompose at C. The compound is sensitive to air and is volatile in highvacuum.

Example 7 Reaction is carried out as in Example except that cobalt (II)chloride is employed. In the course of a disproportioning reactiontris-1r-allyl cobalt is obtained, together with elementary cobalt. Yield20% of theory.

Example 8 A suspension of allyl magnesium chloride is prepared at 0 C.from 20 g.=0.82 g. atom magnesium chips, 350 cc. ether and 60 g.=0.79mol allyl chloride in 100 cc. ether. The suspension is cooled to 30 C.and 28.4 g.=0.18 mol anhydrous chromium (III) chloride ground in 150 cc.ether are then added to form a fine suspension. The chromium (III)chloride disappears and a deep red solution is obtained. The ether isdistilled off in vacuo at low temperatures and the residue is extractedwith pentane at 0 C. The combined pentane extracts are cooled to 80 C.,and deep bright red crystals separate out which, after furtherrecrystallisation, correspond to the composition CrC H and representtris-w-allyl chromium. The compound is sensitive to air and volatile invacuo. Yield 50 to 60% of theory.

Example 9 11 g: 0.05 mol anhydrous nickel bromide are suspended in 50cc. absolute ether and slowly mixed at 80 C. with 500 cc. of an 0.29standard Grignard solution obtained from cinnamyl chloride andmagnesium. When the reaction has finished the ether is drawn off invacuo at a bath temperature of 30" C. and the residue is then extractedat C. with absolute pentane. The yellowish-red pentane solution iscooled to 80 C., whereby 8 g. reddish-yellow crystals precipitate. Thecomposition of these crystals corresponds to (C H C HNi(biS1rcinnamylnickel) Example 10 8 g.=0.036 mol anhydrous nickelbromide are suspended in 20 cc. absolute ether and reacted at 80 C. with250 cc. of an 0.44 standard Grignard solution produced from 3-bromineoctadiene-(1,7) and magnesium. Working up is effected as in Example 9and after 3 days 1.5 g. yellow crystals corresponding to the composition(C H Ni(bis-vr-octadienyl-nickel) are obtained from the pentane solutionat 80 C. Yield 14% of theory.

Example 11 6 g.=0.027 mol anhydrous nickel bromide are suspended in cc.absolute ether and mixed at 130" C. with 300 cc. of an 0.35 standardGrignard solution produced from 3-chlorocyclohexene and magnesium andprecooled to 80 C. The solution turns very dark in colour. After 10hours the ether is drawn off at 10 to 10- torr and a temperature of 80C. The dark coloured residue is extracted With pentane at -80 C. and thepentane solution is subsequently concentrated. After 2 days, yellowishcrystals which decompose even at -30 to C. and correspond to thecomposition (C H Ni (bis-1r-cyclohexenyl-nickel) can be isolated. Theyield is low.

Example 12 6 g.=0.034 mol palladium chloride are suspended in 30 cc.absolute ether and mixed at 80 C. with 400 cc. of an 0.35 standard allylmagnesium chloride solution. After 6-10 hours the ether is drawn off at80 C. and 10- to 1O torr. 3.2 g. bis-1r-allyl palladium in the form oflight yellow crystals can be isolated from the residue by sublimation at10- torr. Yield approx. of theory.

Example 13 3 g.=0.017 mol palladium chloride are suspended in 20 cc.absolute ether and mixed at C. with cc. of an 0.5 standard methallylmagnesium chloride solution. Working up is effected as in Example 12 and0.36 g. bis-ar-methallyl palladium in the form of yellow crystals isobtained. Yield: 10% of theory.

Example 14 3.6 g.=0.0l4 mol anhydrous platinum chloride are suspended in20 cc. absolute ether and mixed at 60 C. with 140 cc. of an 0.42standard solution of allyl magnesium chloride. The ether solution turnsreddish-yellow. Working up is eifected as in Example 12 and smallamounts of bis-vr-allyl platinum in the form of light yell0W crystalsare obtained.

Example 15 A solution of 22 g.=0.08 mol molybdenum pentachloride in 550cc. absolute ether is added dropwise at 20 C. to a solution of 0.52 molallyl magnesium chloride in 1 litre ether. The mixture is stirred for 24hours. The precipitated magnesium chloride is then filtered off andwashed with ether until the solution is colourless. The filtrate isfreed from ether in vacuo and the residue is extracted with 500 cc.pentane. The filtered pentane solution is cooled to 80 C., 4 g. greenishblack crystals of the composition (Mo(C H being obtained. According tomolecular weight determination, the bis-vr-allyl molybdenum is dimeric.Yield: 20% of theory.

Example 16 9.85 g.=16.9 mol tungsten pentabromide are dissolved in 350cc. absolute ether and added dropwise at 20 C. to a solution of 87 molallyl magnesium chloride in cc. ether. The mixture is stirred for 18hours and then freed from ether in vacuo. The residue is extracted with300 cc. pentane. The filtered pentane is concentrated and the residue isSublimated at 10- torr and a bath temperature of 7075 C. 1.2 g. palebrown crystals of the composition (C H W (tetra-bis-1r-al1yl-tungsten)are obtained. Yield: 20% of theory.

Example 17 23.3 g.=0.1 mol zirconium tetrachloride are suspended inabsolute ether and finely ground in a ball mill. The fine suspensionthus obtained is filled up with absolute ether to 500 cm. cooled to 80C., and then added dropwise, under stirring, to a mixture of 50 g.=0.5mol allyl-magnesiumchloride and 800 cm. ether which has also been cooledto 80 C. The mixture is stirred for a period of 12 hours at -80 C.,filtered at 80 C., and freed from ether at 10- torr and 80 C. Theresidue is extracted three times, each time using 600 cm. absolutepentane. The extracts are also filtered at -40 C. and then concentratedin vacuo to about 300 cm. The solution thus obtained is cooled to 80 C.,whereby the zirconium tetra-1r-allyl separates in the form of reddishblack crystals. 10.2 g.=40% of theory of an analytically pure productare obtained as a first fraction. An additional amount of 7 g. zirconiumtetra-n-allyl can be obtained from the mother liquor.

Total yield: 17.3 g.=67.5% of theory.

Example 18 13.55 g.=0.07 mol vanadium tetrachloride, dissolved in 200cm. absolute pentane, are slowly added at -80 C. under vigorous stirringto 1400 cm. of an 0.5 m. solution of allyl-magnesiu-mchloride in such amanner that the temperature of the mixture does not exceed 70 C. After aperiod of about two hours, the mixture is filtered at about 80 C. andthe ether is distilled off at 10 and a temperature below 60 C. The dry,brown residue is extracted four times, each time using 300 cm. absolutepentane which has been cooled to 60 C., and the extracts are againfiltered at -60 C. The very dark coloured filtrate is free of halogen.It is concentrated at 80 C. and 10 torr to about 100 cm. whereby thetris-1r-allyl-vanadium separates in the form of a very finely dividedcrystal powder. On a frit, the product is washed wtih a small amount ofpentane which has been cooled to 80 C., and is subsequently dried at ltorr. Upon contact with air, the tris-ir-allyl vanadium ignitesimmediately and explodes under inert gas at. temperatures of 40 to 30 C.

Example 19 3O g.=0.08 mol ThCL; are suspended in 500 cm. ether, cooledto 0 C. and mixed, under vigorous stirring, with 1026 cm. of an 0.47 m.solution of C H MgCl in ether. The mixture is stirred for 60 hours at 0C. It is then cooled to 30 C., filtered, and the filtrate freed from allvolatile substances at torr. The residue is extracted at 30 C. inseveral steps with a total amount of 4 liters pentane. The extract isfiltered and concentrated to 200 cm. whereby the 7r-Th(C H separates inthe form of yellow crystals. 4.5 g.=14.3% of theory are obtained.

Calculated: Th, 58.6%. Found: Th, 58.4%.

Example 16.15 g.=0.06 mol NbCl are suspended in 250 cm. ether and aremixed at -78 C. under vigorous stirring with 670 cm. of an 0.56 m.solution of C H MgCl. The mixture is stirred for an additional period of16 hours and subsequently filtered at 50 C., and the filtrate isevaporated to dryness at 10 torr. The residue is extracted with 800 cm.pentane which has been cooled to 50 C., and subsequently, the mixture isagain filtered. The filtrate is free of magnesium salt and contains thegreen colored paramagnetic 1r-Nb(C H Upon further evaporating thesolution, a green colored oil is obtained which, however, does notcrystallize.

Example 21 28 g. TaCl; in 200 cm. pentane are ground in a glass ballmill for a period of 8 hours. The fine suspension is then added to 1.6liters of an 0.5 m. solution of C H MgCl in ether at 80 C., subsequentlyfiltered, and the filtrate evaporated at 10* torr. The residue isextracted in several portions with a total amount of 3 liters pentane at80 C. The residue is dissolved in 300 cm. ether at 80 C. The greensolution contains the paramagnetic Ta(C H The tantalum analysisindicates that the solution is 0.026 molar, i.e., the yield amounts to11% of theory. The 1r-Ta(C H does not appear to crystallize.

A further aspect of this invention resides in the production of valuablederivatives of the 1r-allyl transition metal compounds set forth above.These compounds are generally of the type wherein R to R and Me have thsame meanings as set forth above. In this regard, X is an anion, m and nare each an integer of 1 to 3 and m-l-n' are equal to 2 to 4. It ischaracteristic for the compounds of Formula I that the transition metalsare bound to a vr-allyl system or 11'- allyl systems, and in thesimplest case to the 1r-allyl group as such or their hydrocarbon, i.e.,alkyl, aryl or aralkyl and their cyclic derivatives. A 1r-allyl systemis defined as a grouping of 3 C-atoms, which is bound as a substantiallyplanar system to a central atom in substantially the same manner by wayof all 3 C-atoms.

In the simplest case of the bis-ir-allyl-nickel with an empiricalformula 1r-(C H Ni, this type of bond is represented as follows:

The roentgenographic structural analysis of the corresponding methylderivative, the bis-wr-methallyl nickel, has shown that a sandwich typecompound is involved in which the two methallyl groups are bound to thenickel atom as planar systems in such manner that the CH groups go intothe anti-position:

on2 CHa-Ciij,

CH2 Ni In the compounds of type I, producible in accordance with theinvention, at least one of each such planar 1r-allyl systems is bound toa metal atom.

The metals occur in these compounds in different formal valences, andaccordingly, 1 to 4 of such 1r-allyl systems are bound to the particulartransition metal. Likewise, the possibility exists that 2 of such1r-allyl systems are connected with one another via the subsiituents R Rso that an open-chain system exists, which is bound to the transitionmetal via two 1r-allyl groups.

Some 1r-allyl-Me-X compunds are already known. Thus E. O. Fischer and G.Burger (Z. Naturforsch. 16b, 77 (1961) report 94, 2409 (1961)) have forthe first time described the preparation of the ir-allyl-nickel bromidefrom the extremely poisonous nickel carbonyl and allyl bromide. Theyields were given as only 11% of theory. Also known is the conversion ofbutadiene-iron-tricarbonyl with anhydrous hydrogen chloride (F. J.Impastato and K. G. Ihrman, J. Am. Chem. Soc. 83, 3276 (1961)), whichleads to the formation of a 1r-crotyl-iron-tricarbonyl-chloride.

However, these methods for the preparation of these compounds areunsatisfactory since the reaction products can be obtained only in lowyields and since it is necessary to proceed for their production fromthe generally extremely poisonous metal carbonyls. A furtherdisadvantage of these processes consists therein, that frequenly not thepure compound of the above named type are formed, but that complexesresult in which still further substituents, such as for exampleCO-groups, are contained.

It was found that compounds of the type 1r-allyl-Me-X of the generalFormula II may be produced very easily and with practically quantitativeyields directly from 11'- allyl compounds of the transition metals ofthe sub-groups IVb, Vb, VIb or VIII of the Periodic System having atleast twice the effective grouping.

pat-9H m bonded to Me as for instance in the general Formula II in whichn is at least 2.

I have discovered that these 1r-allyl-Me compounds, in which their-allyl moiety is present at least twice, form 1r-allyl-Me-X compoundswhen reacted, such as by contacting, with an acid of the type HX. Theanionic radical X attaches to the transition metal of the 1r-allylcompound and the liberated H+ splits off one of the allyl radicals andis thus removed.

The reaction in accordance with the invention proceeds with HX accordingto the Equation 1 Thus, for each equivalent HX, one equivalent of allylradical is detached from the transition metal.

In similar manner, the compounds of the type vr-allyl-Me-X may beproduced if one proceeds from complexes of transition metals withexclusive multiple olefins by reacting these with an acid HX. Theexpression p a I-Ni +x Hc1-----= 2 The X in HX signifies an anionicradical to which is bound the hydrogen atom in the sense of thepolarization H X Compounds of the type HX are preferably 3r 0 anhydroushydrogen halides, though also other acid compounds, for example, organicacids and particularly carboxylic acids, as well as phenols,thiophenols, mercaptans, hydrocyanic acid and 1,3-diketones (enol form)may be used.

Furthermore, the rr-allyl-Me-X compounds can also be produced byreacting the 1r-allyl-Me compounds in which the vr-allyl moiety ispresent at least twice, with a halogen in lieu of an acid (H+X). In thiscase, the halogen attaches to the transition metal displacing an allylradical. The reaction in accordance with the invention, using a halogeninstead of an HX compound, proceeds according to the Equation 3 whereinfor each equivalent of halogen reacted, formally one equivalent of allylradical is detached from the transition metal. Preferred halogens areiodine and bromine.

The processes in accordance with the invention are advantageouslycarried out with solutions of the starting materials in solvents inertfor the 1r-allyl metal compounds and the referred to complexes, sincethe reactions proceed in solution precisely stoichiometrically. Suitablesolvents are aliphatic or aromatic ethers, cyclic ethers, saturated oraromatic and halogenated hydrocarbons substantially inert to thesecompounds and complexes. The conversions are preferably carried out attemperatures of from 80 to +100 C.

In most cases the reaction products result at once in crystallized form.In some cases the reaction products are re-crystallized from suitablesolvent solutions.

All operations in the following examples were carried out underexclusion of air and humidity, i.e., under a protective gas, such as forexample argon or nitrogen, since the compounds producible in accordancewith the invention are sensitive to air or humidity.

Example 22 Into a solution of 47 g. bis-w-allylnickel in about 1000 crn.other are introduced slowly under stirring at --80 equimolecularquantities (8.0 l. at 20) of anhydrous hydrogen chloride. The initiallyyellow-orange colored solution therein becomes redbrown. After a shorttime brown crystals of rr-allylnickel-chloride separate from thesolution. The suspension is stirred for another hour at and for thecompletion of the reaction briefly heated up to 20. Again one cools to-80, filters off the crystals and dries them in a vacuum. Obtained are33 g.=73% of the theory.

Product of the composition C H NiC1.

Calculated 43.5%, found 43.3% Ni. From the mother liquor furtherquantities of the compound may be isolated.

Example 23 A solution of 25 g. bis-rr-allylnickel in about 1000 cm.ether is converted at 80 with 4.1 anhydrous hydrogen bromide. Thereaction mixture is Worked up and obtained are 27.0 g.=88% of thetheory.

Product of the composition C H NiBr.

Calculated 32.7%, found 32.4% Ni.

Example 24 A solution of 41.3 g. bis-1r-allylnickel in about 1000 cm.ether is converted at 80 with 7.4 l. (5% excess) anhydrous hydrogeniodide. Obtained are 59 g.=89% of the theory of red crystals of thecomposition C H NiI.

Calculated 25.9%, found 25.6% Ni.

Example 25 According to Example 22 bis-1r-methallylnickel is convertedat 80 with anhydrous hydrogen chloride. From the red-brown reactionsolution are isolated redbrown crystals of the composition C4HqNiCl.

Calculated 39.3% found 39.2% Ni.

Example 26 According to Example 22 is converted an ethereal solution ofbis-rr-crotylnickel at 80 with anhydrous hydrogen chloride. Obtained is,in the form of red-brown crystals, the rr-crotyl-nickelchloride of thecomposition C H NiCl.

Calculated 39.3%, Ni, found 39.5% Ni.

Example 27 According to Example 22 are converted 0.61 g.bis-1rcyclooctenyl-nickel in ethereal solution at 80 with equimolecularquantities (72 cm. at 20) anhydrous hydrogen chloride. The solvent isevaporated and the residue freed from cyclooctene at 10* torr(Torricellian vacuum). Subsequently the residue is re-crystallized froman ether-pentane mixture. The ar-cyclooctenylnickelchloride is obtainedin the form of red-brown crystals of the composition C H NiCl.

Calculated 28.9%, found 28.9% Ni.

Example 28 9 g.:52.4 mMol tris-1r-allylchromiurn are converted in 1.5 l.ether at 80 with l.87==5l.4 mMol anhydrous hydrogen chloride. Themixture is stirred for one hour and subsequently filtered over a G-4frit. At 20 the solvent is removed and the residue subsequently dried at10 torr. The yield of bis-1r-allyl-chromiumchloride amounts to 80%. Asample recrystallized from ether shows the following composition: (Cr(CH Cl) Calculated: Mg, 339.22%; Cr, 30.65%; Cl, 20.95%. Found: Mg, 333%;Cr, 30.48%; Cl, 21.20%.

1 1 Example 29 2.9 g.=15.84 mMol tris-w-allyl-cobalt are converted in250 cm. ether with 355 cm. =15.84 mMol anhydrous hydrogen chloride at80. The reaction mixture is stirred for two hours at -50. Obtained is ared-brown crystallizate, which is isolated at low temperatures andsubsequently dried at 80 and torr. The product was analyzed in thefollowing manner:

The crystals were suspended at --80 in 200 cm. of cold toluene. Themixture then was heated to so that a clear red solution resulted. Attemperatures above --20 the complex already decomposes slowly. 2 cm.each of this solution were analyzed as well as to cobalt as also tohalogen; 2 cm. of the above named solution contained: 0.0357 mMol cobaltand 0.035 mMol chlorine. Accordingly the yield ofbis-1r-allylcobaltchloride amounts to 22.5% and the product is of about98% purity.

Example 12.3 g. bis-cyclooctadiene-nickel-(O) are suspended in 100 cm.toluene and converted at 0 under stirring with 1070 cm. (at 20)anhydrous hydrogen chloride. The solution at once becomes coloreddeep-red, and at the walls of the reaction vessel forms a thin nickelsurface. The red solution is evaporated and the residue recrystallizedfrom methylene-chloride. The red powder, resulted in almost quantitativeyield, corresponds to the composition C H NiCl. It is identified as arr-CYClO- octenylnickelchloride.

Calculated 28.9%, found 28.0% Ni.

Example 31 10.0 g.=36.4 mMol bis-cyclooctadiene-nickel-(O) are suspendedin 50 cm. benzene, and converted at 20 with 2.0 cm. glacial acetic acid(2.1 g.= mMol). Within about 25 minutes the crystals dissolve and afterfurther 20 minutes all volatile constituents are distilled off at 10*torr. The remaining red oil is dissolved in 50 cm. hexane. The solutionis cooled to -70", wherein red-brown crystals are separated.

Yield: 5.5 g.=67% of the theory of 1r-cyclooctenylnickelacetate.

C H O Ni: Calculated M.W. 226.7; Ni, Found M.W. 363; Ni, 25.95%.

Example 32 11.2 g.=40.8 mMol bis-cyclooctadiene-nickel-(O) are suspendedin 75 cm. toluene and converted at 20 with 4.5 cm. ethylmercaptan. Themixture is stirred for 4 hours and subsequently filtered over a 6-4frit. The filtrate is evaporated and the crystalline residue isrecrystallized from a toluene-hexane mixture. The crystals correspond tothe 1r-cyclooctenylnickel-mercaptide of the composition C H SNi. Thered-brown crystals showed the following analysis:

Calculated: Ni, 25.70%; M.W., 228.7 (as dimer 457.4). Found: Ni, 26.0%;M.W., 462.

Example 33 19.6 g.=71.3 mMol bis-cyclooctadiene-nickel-(O) are treatedin 50 cm. benzene with 10 cm. :97.7 mMol acetylacetone. The suspensionis stirred for in all 4-5 days until all crystals have become dissolved.Subsequently all volatile constituents are distilled off at 10 torr andmaximally The residue is dissolved in cm. hexane (about 50) and then thesolution is cooled to 0. Obtained are 13-14 g. of red-brown crystals,which may be Sublimated at 10- torr and Yield: 75% of the theory of thevr-cyclooctenyl-nickelacetylacetonate.

C H O Ni: Calculated C, 58.50%; H, 7.51%; Ni, 22.0%. Found C, 58.18% H,7.97%; Ni, 22.1%.

Example 34 6.44 g.=39.6 mMol cyclooctatetraene-nickel-(O) are convertedin the course of 2 hours at 45--50 with 25 cm.

pure glacial acetic acid. Subsequently all volatile constituents aredistilled off in vacuum. The residue is recrystallized from 250 cm.toluene at Obtained are 5.3 g.=60% of the theory of red crystal needlesof the vr-cyclooctatrienylnickelacetate of the composition c oH zozNi.

Calculated: M.W., 222.8 (or respectively as dimer 445.5); Ni, 26.3%.Found: M.W., 494; Ni, 26.0%.

Example 35 2.05 g.=12.6 mMol cyclooctatetraene-nickel-(O) are heated for5 hours in 25 cm. acetylacetone to 100. One permits to cool and thenfilters the intensely red colored solution. The filtrate is evaporatedat vacuum and the residue is dissolved in hot hexane. Obtained are 0.5g.=15% of the theory of brown crystals of the1r-cyclooctatrienylnickel-acetylacetonate of the composition C13H1 O2Ni.

Calculated: Ni, 2.3 Found: Ni, 22.3%.

Undissolved remain in hexane 1.2 g. nickel-acetylacetonate.

Example 36 50.3 g.=0.31 mMol cyclooctatetraene-nickel(O) are suspendedin 750 cm. toluene and at 80 converted slowly under shaking with 7.55 1.anhydrous hydrogen chloride. One permits thawing to 20 and filters offthe red suspension formed. From the mother liquors further constituentsmay be isolated. In all are obtained 46 g.=% of the theory of reactionproduct of the composition CgHgClNi, i.e., thus1r-cyclooctatrienyl-nicke1 chloride.

Calculated: Ni, 29.5%; C1, 17.85%. Found: Ni, 29.2%; C1, 18.15%.

Example 37 5.5 g.=31.4 mMol tris-1r-allylchromium are dissolved in 350cm. ether and converted at 0 with a solution of 3.99 g.=15.7 mMol iodinein 100 cm. ether. The mixture is stirred overnight at 0 and subsequentlyconcentrated in vacuum to about 50 cm. Brown crystals separate. For thecompletion of the crystallization one cools to and then filters oif thereaction product. One washes with a little ether at -80 and subsequentlyone dries at 10 torr. The yield of bis-1r-allyl-chromiumiodide amountsto 7 g.=% of the theory.

(Cr(C H I) Calculated M.W., 522.13; Cr, 19.92%; I, 48.61%. Found: M.W.,490; Cr, 19.95%; I, 48.25%.

Example 38 Into a solution of 6 .6 g. bis-qr-allylnickel in 400 cm.ether is added drop by drop under stirring at 80, a solution of 11.9 g.iodine in ether, A black precipitation results. The solvent is distilledoff and the residue extracted with fresh ether. The filtered extract iscooled to 80, therein deep-red shining crystals of wr-allylnickeliodideare separated.

Yield: 2.75 g.=25% of the theory.

Calculated: Ni, 25.9%. Found: Ni, 25.4%

Example 39 0.05 g.=27.7 mMol tris-1r-allylcobalt are dissolved in 200cm. ether and converted at -50 to -60 with a solution of 3.52 g.=13.85mMol iodine in 60 cm. ether. The mixture is kept overnight understirring at -80. Therein brown crystals are separated, which arerendered impure by slight quantities of green crystals. Thecrystallizate freed from the solvent is dried at 80 and 10 torr. Thecrystallizate is treated at 80 with 200 cm. cold toluene and the mixtureheated to -30. One filters and obtains a deep-red clear solution. 2 cm.each of the solution obtained were analyzed as to cobalt, orrespectively as to iodine. 2 cm. contained 0.0862 rnMol colbalt, orrespectively 0.0850 mMol iodine. Accordingly, thebiS-1r-2tllYlCOb8ltiOdlCl6 is of 98.7%, while the yield amounts to31.2%. Thi indirect analysis is necessary since the product is notstable at room temperature.

Example 40 1.07 g.=5.65 mMol bis-ar-allyl-palladium are dissolved in 50cc. of ether. There was then passed into this solution, which was cooledto 80 150 cc. of dry H-Cl gas (105 of theory). Thereafter the solvent isdistilled off at 10 torr and the yellow residue is crystallized fromtoluol. There are obtained 08 g.=80% of theory of pure1r-allylpalladiumchlon'de.

Example 41 1.84 g.=4.25 mMol bis-vr-allyl-platinum were dissolved in 50cc. of pentane whereupon the product was reacted at 80 with 120 cc. ofdry HOl gas (107% of theory). A bright yellow compound precipitates,which is difficultly soluble in all normal solvents. After separation ofthe product by filtration, the same is washed with pentane and dried.There is obtained 1.1 g.=94.5% of theory of 1rallyl-platinum chloride.

Example 42 3.1 g.= 12.5 mMoll-allyl-l,2,3,4-tetramethyl-1r-cyclobutenyl-w-allyl-nickel of theformula HaC CH CHz-CH=CH9 H3O w \I/ OHa Ni are dissolved in 50 cc. ofpentane and are reacted at 80 with 325 cc. of dry HCl gas (104% oftheory). There .then immediately precipitates a reddish-brown productfrom which the solvent is removed at 10- torr and nun- CH3 :1 \l/ 8Calculated: Nickel, 24.2% Found: Ni, 24.2%

EXAMPLE 43 3 g.=l3.7 mMol of the biS-1r-fll1yl compound n-C H Ni of thefollowing structural formula are reacted in 100 cc. ether with gaseousHCl at 40 C. Excess HCl as well as the ether are then removed in vacuum.The residue is dried in high vacuum at 20 C.

There are obtained a red oil, the composition of which corresponds tothe empirical formula cmH gNicl and the structure of which correspondsto the H -NMR- Spectrum as well as the IR-Spectrum of the followingformula Calculated: Ni, 22.8%. Found: Ni, 22.3%.

14 Example 44 1.92 g.=7.53 mMol tetra-w-allylzirconium are dissolved in200 cc. ether at C. The reaction vessel is evacuated, whereupon 337.6 Ncc.=0.55 g.=15.06 mMol of dry HCl gas is admitted with stirring andvigorous cooling. Upon termination of the reaction the solution isconcentrated to about 50 cc. whereby thebis-1r-allylzirconium-dichloride precipitates in the form of fine, lightyellow crystals. The crystals are collected on a clay plate at lowtemperatures, washed with a little cold ether and then dried in vacuumon the plate. There is obtained 1.2 g.=4.92 mMol of the product, i.e.the yield is 65% of theory. The yield may be increased by furtherconcentrating the filtrate. The bis-1r-allylzirconium-dichloridedecomposes at 20 C. in the course of a few hours. On reaction withalcohol there are obtained 2 Mol propylene per gram atom zirconium.

Example 45 2.33 g.=24.8 mMol phenol are dissolved in 50 cc. of ether andadded dropwise at 40" C. to a solution of 4.35 g.=24.8 mMol oftris-1r-al1ylchromium in cc. of ether. The mixture is kept at 10 C. for12 hours. Brownish crystals are precipitated thereby. The mixture iscooled to 80 C. and the crystals are separated. The residue is Washedwith small amounts of ether and dried at 80 C. and 10- mm. Hg. There areobtained 3.9 g.=70% of theory of bis-1r-allylchromiumphenolate in theform of brownish crystals which correspond to 3 5)2 e 5)- Example 460.93 g.=2.66 mMol of tetra-w-allyl-tungsten dissolved in 50 ml. ofpentane are reacted at 80 C. with 70 cc.=2.66 mMol of gaseous hydrogenchloride. The mixture is warmed up to 30 C., while vigorously stirring.A yellow precipitate is formed which is separated and dried at 10- mm.Hg. There are obtained 0.7 g.=77% of theory of tris-1r-allyl-tungstenchloride which corresponds to (C H WCl.

The properties, activity and reactivity of the 1r-allyl metal compoundsherein described are solely due to the qr-allyl linkage and theparticular stereo positioning of atoms thereby defined. Thus, theireflfective grouping which is controlling for said properties, activityand reactivity is in which Me is a transition metal as defined above,and in which X is an anionic acid radical and preferably halogen, n isan integer of 1-4, m and it each designating an integer of 1-3, withm+n' being 2-4. For this reason, any particular substituent orsubstituents are generally not material in either the conversion of thear-allyl-Me to its salt compound or to their catalytic or otherproperties or reactivities. This is well illustrated by the fact thatshort and long chain aliphatic substituents, cyclic substituents,including those of the bulky pinenyl and various aromatic substituents,all as shown by the at-times highly substituted examples, do not affectthe basic properties of these vr-allyl-Mes.

It is still a further aspect of this invention to provide derivatives ofeither the 1r-allyl transition metal compounds according to Formula I orthe salt derivatives according to Formula II, or both, by adding to saidcompound and/or salt at least one Lewis acid and/or Lewis base. Lewisacids within the meaning of this invention are illustrated by R AlY,lMlY and AlY wherein R is at least one member of the group consisting ofalkyl, cycloalkyl, aralkyl and aryl, and Y is at least one member of thegroup consisting of chloride, bromide and iodide. Lewis bases areillustrated by phosphines, phosphites, phosphorus triamides, arsines,arsinites, arsenic triamides, stibines, stibites, antimony triamides,bismuthines, bismuthites, bismuth triamides and sulfoxides; and inparticular, Lewis bases such as triphenyl-phosphine,tricyclohexyl-phosphine, diphenyl-phosphine, triisopropylphosphine,trimethylphosphite, tris-(o-oxydiphenyl)phosphite,tri-o-cresyl-phosphite, triphenyl-arsine and phosphoricacid-tridiethylamide, or Lewis acids such as aluminum trichloride,aluminum tribromide, ethyl aluminum dichloride, and diethyl aluminummonochloride.

The vr-allyl transition metal compounds, salts and Lewis acid and/orbase derivatives thereof all have been found to catalyze the reactionsof olefins (monoand/or diolefins) and particularly, to catalyze thecyclooligomerization thereof.

It is within the scope of this invention to produce compounds of FormulaII in dimeric form. It is further possible to produce chain oligomers ofsuch compounds, for example, dimers, trimers and/or tetramers, etc.These oligomers depend upon at least two allyl groups being present inthe allyl-containing portion of the compound.

The following examples are further illustrative of the practice of thisinvention.

Example 47 Into a mixture of 1.57 g. tris-bicycloheptene-nickel- (O) in100 cm. toluene is added drop by drop at 30 C. a solution of 6.1 g.allyl-bromide in toluene under stirring. Obtained is a deep red solutionwhich is warmed to room temperature and then filtered. The solvent isdistilled off in vacuum and the residue dried at 10 torr. The product isrecrystallized from ether, and obtained is a red powder of thecomposition i.e., it is a 1r-8llYl-I11Ck6l-bl0l1'lld6 to which is stillcomplex-bound a bicycloheptene molecule.

Calculated: Ni, 21.4%. Found: Ni, 21.0%.

Example 48 A suspension of 4.9 g. bis-cyclooctadiene-nickel-(O) in 100cm. toluene is converted at 20 C. with a solution of 2.7cinnamylchloride in toluene under stirring. Subsequently, the suspensionis stirred for two hours at to C. Toluene and cyclooctadiene aredistilled off in vacuum and the residue dried at l0- torr. The reactionproduct is dissolved in ether, filtered, and the clear solution cooledto 80 C. Therein the 1r-cinnamylnickelchloride is separated in the formof red shining crystals of the composition C H CINi.

Calculated: Ni, 27.8%. Found: Ni, 27.8%

Example 49 According to Example 48, biscyclooctadiene-nickel- (O) isconverted with l-chlorocyclohexene-(Z). Obtained is a red solution whichcontains the 1r-cyclohexyl-nickelchloride.

Example 50 According to Example 48, bis-cyclooctadiene-nickel isconverted with cyclododecatrienyl-chloride. Obtained is a red solutionwhich contains a 1r-cyc1ododecatrienylnickel-chloride.

Example 51 8.4 g.=30.5 mMol biscyclooctadiene-nickel-(O) are dissolvedin 30 cc. of toluene and there is dropwise added at 40 C. 3.5 g.=24.1mMol of 3-chlor-cyclopentene. In the course of the addition, the yellowsolution turns dark red. Traces of metallic nickel were separated andremoved. The clear solution is concentrated to dryness after 36 hours at10- torr. The red colored residue is extracted with pentane. There thenremains undissolved the 1r-cyclopentenyl-nickel-chloride. The red prod-16 net is filtered 011 and dried. There are then obtained 3.5 g.=71.5%of theory of 1rcyclopentenyl-nickelchloride Calculated: Ni, 36.4%.Found: Ni, 36.8%.

Example 52 6.1 g.=22.2 mMol bis-cyclooctadiene-nickel-(O) are dissolvedin 50 cc. of toluene, whereupon there is added at 20 C. 4.1 g.=24.5 mMolof benzyl-allylchloride [1phenyl-4-chlor-butene-(2)] dissolved in 40 cc.of toluene. The yellow colored solution turns red. The toluene isremoved at 10 torr and the orange-red colored residue is then extractedwith pentane. The red colored product is then filtered off and dried invacuo. There are obtained 4 g.=% of theory of thebenzyl-1r-allylnickelchloride.

Calculated: Nickel, 26.94%. Found 25.6%

Example 53 82.0 g.=0.3 Mol of biscyclooctadiene-nickel-(O) are suspendedin 300 cc. of ether, whereupon there is added at 20" C. with vigorousstirring, a solution of 40 g. =0.33 Mol of allylbromide within a periodof 3-4 hours. After the reaction is completed, the mixture is cooleddown to -80 C. There then precipitates the ar-allyl-nickelbromide whichis filtered 01f.

Calculated: Ni, 32.6%. Found: Ni, 32.2%.

Example 54 23 g.=83.6 mMol bis-cyclooctadiene-nickel-(O) are suspendedin 50 cc. of ether and are then admixed at -20 C. in the course of 15hours with a solution of 19.8 g.=92.2 mMol myrtenyl-bromide in 50 cc.ether with stirring. After about 36 hours, the starting complex materialhas been converted. The solution is filtered at 20" C. and is thereaftercooled to 80 C. The red crystals separate. They are filtered off at alow temperature and are dried at 10- torr. There is obtained 10.5 g.=46%of theory of pure r-pinenyl-nickelbromide.

Example 55 Example 56 3.75 g. vr-allyl-nickeliodide are converted in cm.ether at 80 C. with 4.33 g. triphenylphosphine (mol ratio 1:1). Oneheats briefly to 20 C. and then filters oil? the complex resulting inthe form of red-brown crystals (1r-C H NiI-P(C H Yield: 5.7 g.=70% oftheory. Calculated: Ni, 12.0%. Found: Ni, 12.1%.

Example 57 4.2 g. 1r-allyl-nickeliodide are converted according toExample 56, however, with 5.17 g. tricyclohexylphosphine. Obtained islikewise a red-brown crystallizate, which corresponds to the compositionCalculated: Ni, 11.55%. Found: Ni, 11.35%.

Example 58 3.38 g. 1r-allyl-nicke1iodide are converted according toExample 56, hoWCVcr, with 8 g. tris-(o-oxydiphenyl)- 17 phosphite.Obtained is a red-brown crystallizate of the composition 1T-C3H P(OC6H4C5H5 3 Calculated: Ni, 7.70%. Found: Ni, 7.55%.

Example 59 A lzlzl-adduct of 1r-allyl-nickeliodide,triorthocresylphosphite and ethyl aluminum-dichloride was prepared bydissolving 2.54 mMols of ar-allyl-nickeliodide, 2.54 mMols oftriorthocresyl-phosphite and 5 mMols ethyl aluminumdichloride in 150 ml.of chlorobenzene.

Example 60 A 1:1:l-adduct was produced by dissolving 2.04 mMols of alzl-addition product of triphenyl-arsin and 1r-allyl-nickeliodidetogether with 4.1 mMols of ethyl aluminum-dichloride in 100 cc. ofchlorobenzene.

The following list of compounds is exemplary of the class of compoundswhich are producible according to the processes described above andwithin the scope of this invention:

tris- (1r-allyl) -chromium bis-(1r-allyl)-chromium-iodide bis-(1r-allyl-chromium-chloride tris-(1r-allyl)-cobalt bis-(1r-allyl) -cobalt-iodidebis-(vr-allyl)-cobalt-chloride 1r-cyclooctatrienyl-nickel-chloride1r-cyclooctenyl-nickel-chloride 1r-allyl-nickel-iodidear-allyl-nickel-bromide 1r-pinenyl-nickel-bromiderr-crotyl-nickel-iodide wr-cinnamyl-nickel-chloride1,2,3-triphenyl-1r-cyclopropenyl-nickel-bromide1r-allyl-palladium-chl0ride 1r-allyl-nickelchl0ride tetra-(1r-allyl)-zirconium trisar-allyl -vanadium ar-allyl-nickel-chloride compound ofthe formula C H NiCl 1r-cyclododecadienyl-nickel-chloride1rcyclohexenyl-nickel-chloride 1r-cyclododecatrienyl-nickel-chloride1r-cyclopentenyl-nickel-chloride benzyl-ar-allyl-nickel-chloridebis-(r-methallyD-nickel 1r-methallyl-nickel-chloride bis- (rr-crotyl)-nickel bisar-cyclooctenyl -nicke1 1r-cyclooctenyl-nickel-acetatear-cyclooctenyl-nickel-mercaptide 1r-cyclooctenyl-nickel-acetylacetonate1r-cyclooctatrienyl-nickel-acetate1r-cyclooctatrienyl-nickel-aoetylacetonate bis- (ar-allyl -palladiumbis- (w-allyl) -platinuml-allyl-1,2,3,4-tetramethyl-1r-cyclobutenyl-w-allyl-nickel 1 allyl1,2,3,4 tetramethyl 1r cyclobutenyl nickelchloride1,6-di-1r-ally1-hexen-3-yl-nickel1-1r-allyl-nonadiene-3,7-yl-nickel-chloridebis-(vr-allyl)-zirconium-dichloride biswr-allyl -chromium-phenolatetetra- (1r-allyl) -tun'gsten tris-(w-allyl)-tungsten-chloridetris-(1r-allyl) -iron bis- (1r-cinnamyl -nickelbis-(1r-octadienyl)-nickel bis- (1r-methallyl -palladium [bis-(r-allyl-molybdenum] 2 bis-(1r-cyclohexenyl) -nickel tetra- (qr-allyl -thoriumtetra- (-lr-allyl -niobium tetra-( qr-allyl) -tantalum adduct of bis (1rallyl) chromium chloride and ethyl aluminum-dibromide adduct ofbis-(1r-allyl)-cobalt iodide and ethyl-aluminumdichloride adduct ofbis-(w-allyD-cobalt chloride and diethyl-aluminum chloride adduct ofbis-(1r-allyl)-cobalt-chloride and ethyl-aluminum dichloride adduct of1r-allyl-nickel iodide and ethyl-aluminum dichloride adduct ofwr-allyl-nickel iodide and triphenylphosphine adduct of1r-allyl-nickel-iodide, triphenylphosphine andethyl-aluminurn-dichloride adduct of 1r-allyl-nickel-iodide,triphenylph'osphine and aluminum-bromide adduct of 1r allyl nickeliodide and tricyclohexylphosphine adduct of 1r-allyl-nickel-iodide,tricyclohexyl-phosphite and ethyl-aluminum-dichloride adduct ofar-allyl-nickel-iodide, tricyclohexyl-phosphine andethyl-aluminum-dichloride adduct of 11' allyl nickel iodide andtris-(ortho-oxydiphenyl) -phosphite adduct of 1r allyl nickel iodide,tris(-o-oxydiphenyl)- phosphite and ethyl-aluminum-dichloride adduct of1r-pinenyl-nickel-bromide and tricyclohexylph-osphine adduct of1r-pinenyl-nickel-bromide, tricyclohexyl-phosphine and aluminum-bromideadduct of 1r-allyl-nicke1-bromide, triisopropyl-phosphine andaluminum-bromide adduct of ar-allyl-nickel-bromide, phosphoric acidtri-(N- diethyD-arnide and ethyl aluminum-dichloride adduct of1r-allyl-nickel-i-odide, tri-(o-cresyl)-phosphite andet-hyl-aluminum-dichloride adduct of ar-allyl-nickel-bromide andtriethyl-phosphine adduct of 1r-allyl-nickel-bronride,triethyl-phosphine and aluminum-bromide adduct of1r-allyl-nickel-iodide, triphenyl-arsine and ethylaluminum-dichlorideadduct of Ir-CIOiYl-IliCkGl-iOdidG and ethyl-aluminumdichloride addductof 1r-cinnamyl-nickel-chl'oride, diphenyl-phosphine andethyl-aluminum-dichloride adduct of1,2,3-triphenyl-1r-cyclopropenyl-nickel-bromide and aluminum-bromideadduct of 1r-allyl-palladium-chloride and ethyl-aluminum-dichlorideadduct of 1r-allyl-nickel-chloride and ethyl-aluminumdichloride adductof 1r-allyl-nickel-bromide and aluminum-bromide What is claimed is:

1. 1:1:1 adducts of Lewis acids, Lewis bases and ar-allyl transitionmetal compounds.

2. 1:1:1 adducts as claimed in claim 1, wherein said Lewis acid is atleast one member selected from the group consisting of R AlY, RAlY- andAlY wherein R is at least one member selected from the group consistingof alkyl, cycloalkyl, aralkyl and aryl and Y is at least one memberselected from the group consisting of chloride, bromide and iodide.

3. 121:] adducts as claimed in claim 1, wherein said Lewis acid is atleast one member selected from the group consisting of aluminumtrichloride, aluminum tribromide, ethyl aluminum dichloride and diethylaluminum monochloride.

4. 1:1:1 adducts as claimed in claim 1, wherein said Lewis base is atleast one member of the group consisting of phosphines, phosphites,phosphorus triamides, arsines, arsinit-es, arsenic triamides, stibines,stibites, antimony triamides, bismuthines, bismuthites, bismuthtriamides and sulfoxides.

5. 1:1:1 adducts as claimed in claim 4, wherein said member has as atleast one substituent thereon alkyl, cycloalkyl, aryl and aralkyl groupshaving up to about 12 carbon atoms therein.

6. 121:1 adducts as claimed in claim 5, wherein all of the substituentson each member are the same.

7. 1:1:1 adducts as claimed in claim 1, wherein said Lewis base is atleast one selected from the group consisting of triphenylphosphine,tricyclohexyl phosphine, diphenyl phosphine, triisopropyl phosphine,tri-n-butylphosphine, triethylphosphine, trimethylphosphite,tris-(ooxydiphenyl)-phosphite, tri-o-cresylphosphite, triphenylarsineand phosphoric acid tridiethylamide.

8. 1:1:1 adducts as claimed in claim 1, wherein said 1r-allyl transitionmetal compound is at least one compound of the formula R: 1'33 $4 WSZIQIIQT wherein X is an anion; Me is a transition metal selected fromthe group consisting of metals of Groups IVb, Vb, VIb and VIII of thePeriodic Table; n is to 3; m is 1 to 4; m+n is 2 to 4; y is 1 to 2; andR to R are each a substituent selected from the group consisting ofhydrogen, alkyl, cycloalkyl, aralkyl, aryl and R and R together withsaid allyl group from a closed aliphatic hydrocarbon ring.

9. 12111 adducts as claimed in claim 8, wherein said transition metal isa member of the group consisting of titanium, zirconium, vanadium,niobium, tantalum, chromium, molybdenum, tungsten, nickel, iron, cobalt,palladium, platinum, and thorium.

10. 1:1:1 adducts as claimed in claim 8, wherein said X is at least onemember selected from the group consisting of chloride, bromide andiodide.

11. 1:1:1 adducts as claimed in claim 8, wherein said alkyl is selectedfrom the group consisting of methyl and n-pentyl, cycloalkyl iscyclohexyl, aryl is phenyl, and said aliphatic hydrocarbon ring hasabout 4 to 12 carbon atoms therein.

12. 11111 adducts as claimed in claim 8, wherein said allyl moiety is atleast one member of the group consisting of allyl, methallyl, crotyl,cinnamyl, pinenyl, triphenylcyclopropenyl, hexenyl, cyclooctenyl,cyclooctatrienyl, cyclododecatrienyl, cyclobutenyl, dodecatrienyl,octadienyl and cyclohexenyl.

13. Adducts of Lewis acids and ar-allyl transition metal compounds.

14. Adducts as claimed in claim 13, wherein said Lewis acid is at leastone member selected from the group consisting of R AlY, RAIY and AlYwherein R is at least one member selected from the group consisting ofallyl, cycloalkyl, aralkyl and aryl, and Y is at least one memberselected from the group consisting of chloride, bromide and iodide.

15. Adducts as claimed in claim 13, wherein said Lewis acid is at leastone selected from the group consisting of aluminum trichloride, aluminumtribromide, ethyl aluminum dichloride, and diethyl aluminummonochloride.

16. Adducts as claimed in claim 13, wherein said 1r-allyl transitionmetal compound is at least one of the formula wherein X is an anion; Meis a transition metal selected from the group consisting of metals ofGroup IVb, Vb, VIb and VHI of the Periodic Table; n is 0 to 3; m is 1 to4; m+n is 2 to 4; y is l to 2; and R to R are each a substituentselected from the group consisting of hydrogen, alkyl, cycloalkyl,aralkyl, aryl, and R and R together with said allyl group form a closedaliphatic hydrocarbon ring.

17. Adducts as claimed in claim 13, wherein said transition metal is amember of the group consisting of titanium, zirconium, vanadium,niobium, tantalum, chromium, molybdenum, tungsten, nickel, iron, cobalt,palladium, platinum and thorium.

18. Adducts as claimed in claim 13, wherein said X is at least onemember selected from the group consisting of chloride, bromide andiodide.

19. Adducts as claimed in claim 13, wherein said alkyl is selected fromthe group consisting of methyl, and n-pentyl, cycloalkyl is cyclohexyl,aryl is phenyl, and said aliphatic hydrocarbon ring has about 4 to 12carbon atoms therein.

20. Adducts as claimed in claim 16, wherein said allyl moiety is atleast one member of the group consisting of allyl methallyl, crotyl,cinnamyl, pinenyl, triphenylcyclopropenyl, hexenyl, cyclooctenyl,cyclooctatrienyl, cyclododecatrienyl, cyclobutenyl, dodecatrienyl,octadienyl and cyclohexenyl.

21. Adducts of at least one Lewis base selected from the groupconsisting of phosphites, phosphorus triamides, arsines, arsinites,arsenic triamides, stibines, stibites, antimony triamides, bismuthines,bismuthites, bismuth triamides and sulfoxides with 1r-allyl transitionmetal compounds.

22. Adducts as claimed in claim 21, wherein said member has as at leastone substituent thereon alkyl, cycloalkyl, aryl and aralkyl groupshaving up to about 12 carbon atoms therein.

23. Adducts as claimed in claim 22, wherein all of the substituents oneach member are the same.

24. Adducts as claimed in claim 21, wherein said Lewis base is at leastone selected from the group consisting of trimethylphosphite,tris-(o-oxydiphenyl)-phosphite, trio-cresylphosphite, triphenylarsineand phosphoric acid tridiethylamide.

25. Adducts as claimed in claim 21, wherein said Ir-allyl transitionmetal compound is at least one of the formula wherein X is an anion; Meis a transition metal selected from the group consisting of metals ofGroup IVb, Vb, VIb and VIII of the Periodic Table; n is 0 to 3; m is 1to 4; m+n is 2 to 4; y is 1 to 2; and R to R are each a substituentselected from the group consisting of hydrogen, alkyl, cycloalkyl,aralkyl, aryl, and R and R together with said allyl group form a closedaliphatic hydrocarbon ring.

26. Adducts as claimed in claim 25, wherein said transition metal is amember of the group consisting of titanium, zirconium, vanadium,niobium, tantalum, chromium, molybdenum, tungsten, nickel, iron, cobalt,palladium, platinum, and thorium.

27. Adducts as claimed in claim 25, wherein said X is at least onemember selected from the group consisting of chloride, bromide andiodide.

28. Adducts as claimed in claim 25, wherein said alkyl is selected fromthe group consisting of methyl, and n-pentyl, cycloalkyl is cyclohexyl,aryl is phenyl, and said aliphatic hydrocarbon ring has about 4 to 12carbon atoms therein.

29. Adducts as claimed in claim 25, wherein said allyl moiety is atleast one member of the group consisting of allyl, methallyl, crotyl,cinnamyl, pinenyl, triphenylcyclopropenyl, hexenyl, cyclooctenyl,cyclooctatrienyl, cyclododecatrienyl, cyclobutenyl, dodecatrienyl,octadienyl and cyclohexenyl.

References Cited Heck et al., Chem. and Industry (London),

TOBIAS E. LEVOW, Primary Examiner A. P. DEMERS, Assistant Examiner 2223? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 933Dated September 3: 9 9

Inventor s) It is certified that error appears in the above-identifiedpatent and that: said Letters Patent are hereby corrected as shownbelow:

Column 14, line 29, after "claim 1'', delete line 30, delete thestructural formula.

Column 15, line 5, delete the structural formula.

SIGNED AM QZALED EMU-Mk.

mm: B. Anmi OffieQ mimfie m'

